Fluorochemical composition comprising a polymer derived from a fluorochemical urethane (meth)acrylate monomer for imparting stain release properties to a substrate

ABSTRACT

A fluorochemical composition is described comprising a polymer derived from a fluorochemical urethane (meth)acrylate monomer. The fluorochemical composition is useful for imparting stain release properties to a substrate.

FIELD OF THE INVENTION

The present invention relates to fluorochemical compositions for thetreatment of substrates, in particular fibrous substrates such astextiles to impart stain release properties to those substrates.

BACKGROUND OF THE INVENTION

Fluorochemical compositions for the treatment of substrates such asleather, textiles and paper, are well known and are used to impartvarious properties to the substrate such as water and/or oil repellency,waterproofness, anti-staining, and soil-resistance. For example, U.S.Pat. No. 5,100,954 discloses a soil resisting agent containing, as aneffective component, a copolymer of (I) a fluorine-containing urethanecompound containing a (meth)acryloyl group or an allyl group, and apolyfluoroalkyl group, obtained by reacting (a) a polyfunctionalisocyanate having at least trifunctionality, (b) a hydroxy compoundcontaining a (meth)acryloyl group or an allyl group, and (c) a hydroxycompound having a polyfluoroalkyl group, and (II) a copolymerizablecompound other than said fluorine-containing urethane compound.

U.S. Pat. No. 4,920,190 describes certain fluorochemical compositionsthat are based on polymers of fluorinated acrylic monomers in which aperfluoroalkyl group is linked by 2,4-toluenediisocyanate to an acrylateor methacrylate. Amongst useful acrylates and methacrylates arementioned mono-(meth)acrylates of polyalkyleneglycols. Thefluorochemical compositions are said to be suitable as water oroil-repellents for various substrates and in particular leather. U.S.Pat. No. 4,778,915 describes certain polymers of fluorinated acrylicmonomers that contain a perfluoroalkyl group linked to an acrylate ormethacrylate by a di-isocyanate, for use as water or oil repellents.

Fluorochemical compositions are also used to facilitate stain or soilrelease from a substrate such as, for example, a fabric. Routinetreatments of fabrics with various modifying additives such assofteners, stiffeners, and lubricants, to impart desired properties to acommercial fabric typically increase the oleophilicity of the fabric,thereby significantly increasing its tendency to accept oily stains andreducing its ability to release such stains after laundering.Fluorochemical compositions based on a mixture of a fluorinated compoundand a non-fluorinated hydrophilic compound or a chemical “hybrid”compound containing fluorochemical oleophobic segments (“F”) andnon-fluorinated hydrophilic segments (“H”) are known to act as stainrelease compositions since they provide oil repellency during normalwear and inhibit wicking or diffusion of oily soils into the fabric orfiber bundles as well as facilitate soil release during laundering.

For example, U.S. Pat. No. 4,859,754 describes certain water and oilrepellent treatments having desoiling properties that are composed of apolyfluorinated group containing copolymer obtained by copolymerizing afirst and second monomer wherein the first monomer contains apolyfluorinated group and the second monomer is an amphiphatic monomerhaving a hydrophilic moiety and a lipophilic moiety.

U.S. Pat. No. 3,920,614 describes certain high soil release oil-andwater repellent copolymers prepared by copolymerization of at least 25%by weight of a fluoroalkyl monomer and 5 to 50% by weight ofpoly(oxyethylene) acrylate or methacrylate.

U.S. Pat. No. 4,695,488 describes certain polymers obtained byhomopolymerization of poly(oxyalkylene) monomers terminated byfluorinated groups. According to the disclosure, a composition based onthis polymer could impart stainproofing properties with good durabilityto a substrate such as plastics, fabric and paper.

Despite the many fluorochemical compositions known to impart stainrelease properties to a substrate, there continues to be a desire forfluorochemical compositions with improved properties. Desirableproperties include easy cleanability of substrates based on naturalfibers such as cotton and blends of cotton and polyester, particularlywith respect to oil type stains (dirty motor oil, vegetable oil) andwater based stains (tea, coffee, wine); low manufacturing cost; highstorage stability; easy emulsifiability and high performance even ifapplied in low quantities. It is also desired that the fluorochemicalcompositions provide good stain release properties and oil and/or waterrepellency properties to the substrate.

SUMMARY OF THE INVENTION

The present invention provides a method of treatment of a substratecomprising the step of contacting said substrate with a fluorochemicalcomposition comprising a polymer derived from polymerization of monomercorresponding to the following general formula (I):

wherein:

R_(f) is selected from the group consisting of perfluorinated orpartially fluorinated aliphatic groups;

L¹ and L² are each independently an organic divalent linking group andthey may be the same or different;

L³ represents an organic linking group with a valence of n+1;

t is 0 or 1;

n is an integer of 2 to 20;

A¹ and A² are each independently selected from the group consisting ofdivalent residues obtained by removing 2 —NCO groups from acorresponding diisocyanate;

X¹ is selected from the group consisting of O, NH and S;

X² is selected from the group consisting of O, NH and S;

B¹ represents a hydrophilic residue obtained by removing the groups HX¹and HX² from a compound HX¹—B¹—X²H that comprises a poly(oxyalkylene)group;

G represents a free radical polymerizable group; and

s is 0 or 1 with the proviso that when s is 0, L² represents ahydrophilic segment comprising a poly(oxyalkylene) group or said polymeris derived from a copolymerization of a monomer according to formula (I)and a poly(oxyalkylene) group containing monomer.

Also provided is a fluorochemical composition comprising a polymerderived from a polymerization of a monomer corresponding to thefollowing general formula (I):

wherein:

R_(f) is selected from the group consisting of perfluorinated orpartially fluorinated aliphatic groups;

L¹ and L² are each independently selected from the group consisting oforganic divalent linking groups;

L³ is an organic linking group with a valence of n+1;

t is 0 or 1;

n is an integer of 2 to 20;

A¹ and A² are each independently selected from the group consisting ofdivalent residues obtained by removing twp —NCO groups from acorresponding diisocyanate;

X¹ is selected from the group consisting of O, NH and S;

X² is selected from the group consisting of O, NH and S;

B¹ represents a hydrophilic segment comprising a poly(oxyalkylene)group;

G represents a free radical polymerizable group; and

s is 0 or 1 with the proviso that when s is 0, L² represents ahydrophilic segment comprising a poly(oxyalkylene) group or said polymeris derived from a copolymerization of a monomer according to formula (I)and a poly(oxyalkylene) group containing monomer.

There is further provided a use of the fluorochemical composition toprovide good stain release properties to a substrate and a substratecomprising on at least one of its surfaces, the fluorochemicalcomposition.

Further provided are a monomer according to formula (I) above and amonomer composition including a monomer according to formula (I) and apoly(oxyalkylene)-containing monomer.

DETAILED DESCRIPTION OF THE INVENTION

The polymer used in the fluorochemical composition is derived from atleast one monomer according to formula (I) above. If the monomeraccording to formula (I) includes a poly(oxyalkylene) group, i.e. s is1, and/or L² contains a polyoxyalkylene a homopolymer of the monomer offormula (I) can be used as well as a copolymer of that monomer. Thepolyoxyalkylene group is typically of a sufficient length such thatsufficient wetting of the substrates occurs during laundering therebyfacilitating removal of stain. Preferably, the number of oxyalkylenemoieties in the poly(oxyalkylene) group is between about 18 and 275 orbetween about 20 and 190 and more preferably between about 23 and 95. Incase the monomer according to formula (I) does not include thepoly(oxyalkylene) group, the polymer is derived from at least a monomerof formula (I) and at least one comonomer that includes apoly(oxyalkylene) group preferably having between about 5 and 16oxyalkylene moieties.

The polymer may further include other ethylenically unsaturatedcomonomers such as vinylacetate, acrylates and methacrylates (e.g.,methyl(meth)acrylate, glycidyl methacrylate, ethyl(meth)acrylate),vinylchloride, vinylidenechlorides, styrenes, acrylic acids, methacrylicacids and acrylonitriles. Other suitable comonomers includeurethane-acrylate or urethane-methacrylate type monomers that can beobtained by the reaction of a diisocyanate and a hydroxy oramino-functionalised acrylate or methacrylate and another hydroxy oramino-functionalised compound such as an isocyanate blocking agent.Particular examples of the latter type of comonomers include thereaction product of a disocyanate, 2-hydroxyethyl(meth)acrylate and2-butanone oxime or the reaction product of a diisocyanate, a mono(meth)acrylate of a polyethylene glycol and 2-butanone oxime.

Typically, the polymer includes between about 25% and 100% based on thetotal number of units in the polymer, preferably between about 40% and100% of units derived from a monomer according to formula (I) thatcontains a poly(oxyalkylene) group.

In case the polymer is derived from monomers according to formula (I)that do not include the poly(oxyalkylene) group, the polymer alsoincludes a comonomer that contains poly(oxyalkylene) groups. In thisinstance, the number of moieties in the polymer derived from monomersaccording to formula (I) not including poly(oxyalkylene) is preferablybetween about 5% and 50%, more preferably between about 15% and 40% andthe number of units derived from a poly(oxyalkylene) containingcomonomer is preferably between about 50% and 95% and more preferablybetween about 60% and 85%.

Description of Preferred Monomers According to Formula (I).

The fluorinated aliphatic group, R_(f), is preferably a fluorinated,stable, inert, preferably saturated, non-polar, monovalent alkyl group.It can be straight chain, branched chain, or cyclic or combinationsthereof It can contain heteroatoms, bonded only to carbon atoms, such asoxygen, divalent or hexavalent sulfur, or nitrogen. R_(f) is preferablya fully-fluorinated alkyl group, but hydrogen or chlorine atoms can bepresent as substituents, but preferably not more than one atom of eitheris present for every two carbon atoms. The R_(f) group typically has atleast about 3 carbon atoms, preferably about 3 to 14 carbon atoms andmore preferably at least about 6 carbon atoms. R_(f) preferably containsabout 40% to 80% fluorine by weight, more preferably about 50% to 78%fluorine by weight. The terminal portion of the R_(f) radical ispreferably a perfluorinated moiety, preferably containing at least about7 fluorine atoms, e.g., CF₃CF₂CF₂—, (CF₃)₂CF—, F₅SCF₂—. Preferred R_(f)groups are fully or substantially fluorinated and are preferably thoseperfluorinated alkyls according to the formula C_(m)F_(2m+1)—where m is3 to 14. A monomer according to formula (I) includes a plurality ofR_(f) groups as indicated by the variable n. Preferably, the monomercontains 3 to 6 or more R_(f) groups. Most preferably, the number ofR_(f) groups in the monomer is between about 4 and 9.

Preferably, t in formula (I) represents 1 and an organic divalentlinking group L¹ is present. Linking groups L¹ include straight chain,branched chain or cyclic alkylene, arylene, aralkylene, oxy, oxo, thio,sulfonyl, sulfoxy, amino, imino, sulfonamido, carbonamido, carbonyloxy,urethanylene, ureylene groups, and combinations thereof such assulfonamidoalkylene or carbonamidoalkylene. A particularly preferredlinking group L¹ is represented by one of the following formulas:

wherein:

R³ is selected from the group consisting of linear or branched alkyleneshaving 2 to 4 carbon atoms, and

R⁴ represents an alkyl having about 1 to 4 carbon atoms, for examplemethyl, ethyl or n-butyl.

L³ is a linking group with a valence of n+1 that preferably correspondsto the following formula:

 wherein:

 n is as defined above,

Z represents the residue of a free radical initiator,

R⁵ is hydrogen or a methyl group,

X⁵ is S,

X⁶is O or NH and

L⁵ represents an alkylene preferably having 2 to 4 carbon atoms.

B¹ is the hydrophilic residue obtained by removing the groups HX¹ andHX² from a compound HX¹—B¹—X²H that comprises a poly(oxyalkylene) group.Suitable poly(oxyalkylene)groups include those of which the oxyalkylenemoiety has 2 to 4 carbons such as —OCH₂—CH₂—, —OCH₂—CH₂—CH₂—,—OCH(CH₃)CH₂—, and —OCH(CH₃)CH(CH₃)—. The oxyalkylene moieties in thepoly(oxyalkylene) group can be the same, as in poly(oxypropylene), orcan be present as a mixture, as in a heteric straight or branched chainpolymer or polymer with randomly distributed oxyethylene andoxypropylene moieties, or as in a straight or branched chain polymerwith blocks of oxyethylene units and blocks of oxypropylene units. Thepoly(oxyalkylene) chain can be interrupted by or include one or morecatenary linkages. Where the catenary linkages have three or morevalences, they provide a means for obtaining a branched chain ofoxyalkylene moieties. The poly(oxyalkylene) group may further contain amixture of oxyalkylene moieties such as a mixture of oxyethylene andoxypropylene. Preferably, the majority of oxyalkylene moieties areoxyethylene, and preferably the number of oxyethylene moieties is atleast about 50% and more preferably at least about 70%. The averagenumber of oxyalkylene moieties is typically between about 18 and 275 andmore preferably between about 25 and 182. B¹ may also include an organicdivalent linking group that links the poly(oxyalkylene) group to X¹ orX². Such organic divalent linking group is preferably a lower alkylenemoiety having between 1 and 4 carbon atoms such as a methylene orethylene moiety. Preferably, B¹ is the hydrophilic residue obtained byremoving the groups HX¹ and HX² from a compound HX¹—B¹—X²H selected fromthe group consisting of poly(oxyalkylene)diols (such aspolyethyleneglycol), poly(oxyalkylene)thiols andpoly(oxyalkylene)diamines.

L² is an organic divalent linking group such as oxy, amino, linear orbranched alkylenes having 1 to 4 carbon atoms or poly(oxyalkylenes)containing a group such as polyethyleneoxide or polypropyleneoxide. Inthe case where s is 0, L² preferably comprises a poly(oxyalkylene) grouphaving between about 5 and 20 oxyalkylene groups.

G is a free radical polymerisable group and is typically anethylenically unsaturated group. Particularly preferred is anα,β-ethylenically unsaturated carbonyl group such as —CO—CH═CH₂ and—CO—C(CH₃)═CH₂. Accordingly, in a preferred embodiment, L²—G togetherrepresent a moiety corresponding to the following formula (II):

 wherein:

X³ and X⁴ each independently are selected from O or NH,

R¹ is a linear or branched alkylene having 2 to 4 carbon atoms or apoly(oxyalkylene) containing group, and

R² is hydrogen or a methyl group.

The monomers according to formula (I) wherein s is 1 are typicallyprepared according to the following general procedure. In a firstreaction, an oligomer containing a plurality of R_(f) groups and afunctionality capable of reacting with an isocyanate is reacted with adiisocyanate. The oligomers can be prepared according to the proceduredescribed in, e.g., U.S. Pat. No. 5,292,796. Typically, theirpreparation involves a free radical polymerisation of a fluorochemicalcompound having an ethylenic unsaturation in the presence of anend-capping agent that includes a functional group capable of reactingwith an isocyanate. Fluorochemical compounds having an ethylenicunsaturation are disclosed, e.g., in U.S. Pat. No. 2,803,615 (Ahlbrechtet al.) and U.S. Pat. No. 2,841,573 (Ahlbrecht et al.). Examples of suchcompounds include general classes of fluorochemical olefins such asacrylates, methacrylates, vinyl ethers, and allyl compounds containingfluorinated sulfonamido groups, acrylates or methacrylates derived fromfluorochemical telomer alcohols, fluorochemical thiols, and the like.Preferred compounds include N-methyl perfluorooctanesulfonamidoethylacrylate, N-methylperfluorooctanesulfonamidoethyl methacrylate,N-ethylperfluorooctanesulfonamidoethyl acrylate,N-methylperfluorohexylsulfonamidoethyl acrylate, perfluorooctylacrylate, N-methyl perfluorooctanesulfonamidoethylvinyl ether, andC₈F₁₇SO₂NHCH₂ CH═CH₂, 2-perfluoroalkyl ethyl(meth)acrylate and otherssuch as perfluorocyclohexyl acrylate. In addition to the fluorochemicalcompound having an ethylenic unsaturation, comonomers such as acrylatesand methacrylates can be used.

Suitable end-capping agents typically include a mercapto group and afunctional group capable of reacting with an isocyanate. Such functionalgroups include hydroxy and amino. Examples of end-capping agents include2-mercaptoethanol, 11-mercaptoundecanol, 3-mercapto-2-butanol,1-mercapto-2-propanol, 2-mercaptopyridinol, o-, m-, and p-thiocresol and2-mercaptoethylamine. Preferred functionalized end-capping agentsinclude 2-mercaptoethanol, 4-mercaptobutanol and 2-mercaptoethylamine.

Suitable diisocyanates that can be used include aromatic diisocyanatessuch as 4,4′-methylenediphenylenediisocyanate,4,6-di-(trifluoromethyl)-1,3-benzene diisocyanate,2,4-toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylenediisocyanate, 4,4′-diisocyanatodiphenylether,3,3′-dichloro-4,4′-diisocyanatodiphenylmethane,4,5′-diphenyldiisocyanate, 4,4′-diisocyanatodibenzyl,3,3′-dimethoxy-4,4′-diisocyanatodiphenyl,3,3′-dimethyl-4,4′-diisocyanatodiphenyl,2,2′-dichloro-5,5′-dimethoxy-4,4′-diisocyanato diphenyl,1,3-diisocyanatobenzene, 1,2-naphthylene diisocyanate,4-chloro-1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, and1,8-dinitro-2,7-naphthylene diisocyanate; alicyclic diisocyanates suchas 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate;3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate; aliphaticdiisocyanates such as 1,6-hexamethylenediisocyanate,2,2,4-trimethyl-1,6-hexamethylenediisocyanate, and1,2-ethylenediisocyanate and cyclic diisocyanates such as isophoronediisocyanate (IPDI). Also, other diisocyanates such as those availablefrom Bayer under the trademark DESMODUR™ can be used, for exampleDESMODUR™ TT and DESMODUR™ W.

In a second reaction separate from the above reaction, a diisocyanatewhich may be the same or different as the one used in the abovedescribed reaction, is reacted with a monomer that contains a groupcapable of reacting with an isocyanate such as hydroxy or amino.Preferred monomers are acrylates, methacrylates, acrylamides andmethacrylamides. Especially preferred monomers correspond to thefollowing formula:

wherein:

X³ and X⁴ are each independently selected from O or NH,

R¹ is a linear or branched alkylene having 1 to 4 carbon atoms or apoly(oxyalkylene) containing group, and

R² is hydrogen or a methyl group.

Specific examples include 2-hydroxyethyl(meth)acrylate,3-hydroxypropyl(meth)acrylate, 6-hydroxy-hexyl(meth)acrylate, mono(meth)acrylates of a polyethylene glycol, mono (meth)acrylates of ablock copolymer of ethylene oxide and propylene oxide; mono(meth)acrylates of amino-or diamino- terminated polyethers and mono(meth)acrylates of tetramethylene oxide glycols.

The reaction products of the above described first and second reactioncan then be combined and reacted with a compound of the formulaHX¹—B¹—X²H. Suitable compounds of the latter formula are describedherein. The reaction conditions that can be employed in each of thesethree reactions are the conventional reaction conditions employed inreacting an isocyanate. Preferably the reactions are run in the presenceof a catalyst. Suitable catalysts include tin salts such as dibutyltindilaurate, stannous octanoate, stannous oleate, tin dibutyldi-(2-ethylhexanoate), stannous chloride; and others known to those skilled in theart. The amount of catalyst present will depend on the particularreaction, and thus it is not practical to recite particular preferredconcentrations. Generally, however, suitable catalyst concentrations arefrom about 0.001 percent to 10 percent, preferably about 0.1 percent to5 percent, by weight based on the total weight of the reactants.

The condensation reactions are preferably carried out under dryconditions in a polar solvent such as ethyl acetate, acetone, methylisobutyl ketone, toluene and the like. Suitable reaction temperatureswill be easily determined by those skilled in the art based on theparticular reagents, solvents, and catalysts being used. While it is notpractical to enumerate particular temperatures suitable for allsituations, generally suitable temperatures are between about roomtemperature and about 120° C.

Monomers according to formula (I) wherein s is 0 can be prepared in asingle step by reacting the fluorochemical oligomer and a monomer thatcontains a group capable of reacting with an isocyanate such as hydroxyor amino with a diisocyanate. Suitable diisocyanates, monomerscontaining a group capable of reacting with an isocyanate and thefluorochemical oligomers are described herein.

As described herein, where the monomer according to formula (I) does notinclude a polyoxyalkylene group, the polymer is derived from acopolymerisation of a monomer according to formula (I) and a comonomercontaining a poly(oxyalkylene) group. The comonomer containing apoly(oxyalkylene) group can be a monomer corresponding to formula (I)with s being 1 or L² containing a poly(oxyalkylene) group, butpreferably it is a monomer that does not contain a fluorochemical group.Preferred comonomers correspond to the following formula:

wherein:

R⁶, R⁷ and R⁸ are each independently selected from the group consistingof linear or branched alkylenes having 2 to 4 carbon atoms;

R⁹ is hydrogen or an alkyl group having 1 to 4 carbon atoms;

x and y are each independently an integer of 0 to about 30, typically 0to about 20 and preferably 0 to about 16, and the sum of x and y is atleast about 5;

and R¹⁰ is hydrogen or a methyl group.

Examples of comonomers containing a poly(oxyalkylene) group include mono(meth)acrylates of a polyethylene glycol, mono (meth)acrylates of ablock copolymer of ethylene oxide and propylene oxide; mono(meth)acrylates of amino- or diamino-terminated polyethers and(meth)acrylates of methoxypolyethyleneglycols.

The polymer of the fluorochemical composition is typically prepared byfree radical polymerisation e.g. by solution- or emulsion polymerizationtechniques. The polymerisation can be a thermal or photochemicalpolymerisation. Useful free radical initiators are known in the art andinclude azo compounds, such as azo(bis)-isobutyronitrile andazo(bis)-2-cyanovaleric acid, hydroperoxides such as cumene, t-butyl andt-amyl hydroperoxide, dialkyl peroxides such as di-t-butyl anddicumylperoxide, peroxyesters such as t-butylperbenzoate anddi-t-butylperoxy phtalate, diacylperoxides such as benzoyl peroxide andlauryl peroxide.

The fluorochemical composition is soluble in various organic solventssuch as ethyl acetate, ethers (di-propylene glycol mono methyl ether,tetrahydrofuran, ethylene glycol ethers), ketones (acetone, methyl ethylketone, methyl isobutyl ketone), alcohols (methanol, ethanol, isopropylalcohol, glycols), dimethylpyrrolidone and mixtures thereof Accordingly,the fluorochemical composition can be used as a solution in an organicsolvent or alternatively, an emulsion of the fluorochemical compositionin water can be prepared according to well-known techniques. Forexample, a solution of the fluorochemical composition in an organicsolvent, e.g. ethylacetate, gradually can be added to a solution of anemulsifier in water with vigorous stirring. The thus obtained pre-mixmay then be subjected to ultrasound treatment or high shearhomogenization to obtain a milky to transparent emulsion of thefluorochemical composition in water. If desired, the organic solvent canthen be removed e.g. by distillation under reduced pressure.

The fluorochemical composition of this invention can be applied usingconventional application methods but is preferably used as an aqueousemulsion. Alternatively, it can be used as a treatment composition insolvent. An aqueous emulsion will generally contain water, an amount offluorochemical composition effective to provide repellent properties toa substrate treated therewith, and a surfactant in an amount effectiveto stabilize the emulsion. Water is preferably present in an amount ofabout 70 to 2000 parts by weight based on 100 parts by weight of thefluorochemical composition of the invention. The surfactant ispreferably present in an amount of about 1 to 25 parts by weight,preferably about 2 to 10 parts by weight, based on 100 parts by weightof the fluorochemical composition. Conventional cationic, nonionic,anionic, and zwitterionic surfactants are suitable.

The amount of the treating composition applied to a substrate inaccordance with this invention is chosen to impart the desired stainrelease properties to the substrate surface. Typically, an amount oftreating composition sufficient to provide about 0.01% to 5% by weight,preferably about 0.05% to 2% by weight, based on the weight of thesubstrate, of fluorochemical composition on the treated substrate issufficient. The amount which is sufficient to impart desired stainrelease can be determined empirically and can be increased as necessaryor desired.

To the fluorochemical composition of the invention there may also beadded other fluorinated products, polymers or auxiliary products such asstarch, dextrin, casein, polyvinyl alcohols, cellulose and cellulosederivatives such as cellulose ethers, copolymers of (meth)acrylic acidand alkyl esters of (meth)acrylic acid, polyglycols such polyethyleneglycols, sizing agents, materials to improve water and/or oilrepellency, fire proofing or antistatic properties, buffering agents,fungicidal agents, optical bleaching agents, sequestering agents,mineral salts, surface-active agents, or swelling agents to promotepenetration.

Particularly suitable auxiliary products for use in the fluorochemicalcomposition include polyvinyl alcohols, polyethylene glycols, non-ioniccellulose ethers and copolymers of an alkyl (meth)acrylate and(meth)acrylic acid. It was found that in many cases, these auxiliaryproducts improve the stain release performance of the fluorochemicalcomposition. Preferred polyvinyl alcohols are polyvinyl alcohols havinga degree of hydrolysis of at least about 65% by weight and morepreferably a degree of hydrolysis of at least about 80% by weight.

Examples of non-ionic cellulose ether derivatives include methylcellulose, hydroxypropyl cellulose and methylhydroxypropyl cellulose.Particularly preferred cellulose ethers are hydroxyalkyl celluloseethers. Preferably, the etherified cellulose is highly hydrophilic.Accordingly, cellulose ethers that contain large hydrophobicsubstituents, such as the hydrophobically modified cellulose etheravailable from Aqualon under the trademark NEXTON™, are not preferredfor use in the fluorochemical composition of this invention.

The polyethylene glycols useful as additives are preferably homopolymersof ethylene oxide and typically have a molecular weight between about200 and 5000.

Preferred copolymers of an alkyl(meth)acrylate and (meth)acrylic acidare copolymers in which the weight ratio of (meth)acrylic acid to thealkyl(meth)acrylate is between about 20:80 and 90:10. More preferably,the weight ratio is between about 50:50 and 85:15. It is furtherpreferred that the alkyl group of the (meth)acrylate monomer is a loweralkyl group having about 1 to 6 carbon atoms. Examples of alkyl(meth)acrylate monomers include, methyl, ethyl and n-butyl acrylates andmethacrylates. The copolymer of an alkyl (meth)acrylate and(meth)acrylic acid may further contain moieties derived fromethylenically unsaturated monomers, but preferably, the copolymer onlyconsists of moieties derived from alkyl (meth)acrylates and(meth)acrylic acid. The copolymer may also be partially or fullyneutralised with a base such as sodium hydroxide or ammonium hydroxide.

The substrates treated with the fluorochemical composition of thisinvention are not especially limited and include plastic, metal, glass,fibrous materials such as textile fabrics, wood, non-wovens and paper.The fluorochemical composition is particularly useful for impartingstain release properties to a substrate that comprises natural fibers,in particular a substrate that consists of cellulose fibers or asubstrate consisting of cellulose and polyester fibers. Substratestreated with a fluorochemical composition of this invention haveparticular good stain release properties for dirty motor oil stains andtea stains.

In order to affect treatment of a textile substrate, the substrate canbe immersed in a diluted emulsion. The saturated substrate can then berun through a padder/roller to remove excess emulsion, dried and curedin an oven at a temperature and for a time sufficient to provide a curedtreated substrate. This curing process is typically carried out attemperatures between about 50° C. to 190° C. depending on the particularsystem or application method used. In general, a temperature of about120° C. to 170° C., preferably about 150° C. to 170° C. for a period ofabout 20 seconds to 10 minutes, preferably 3 to 5 minutes, is suitable.The cured treated substrate can be used as desired, e.g., incorporatedor fashioned into a garment.

The invention is further illustrated by reference to the followingexamples without however the intention to limit the invention thereto.

EXAMPLES

Formulation and Treatment Procedure

Treatment baths were formulated containing a defined amount of thefluorochemical treatment agent. Treatments were applied to the testsubstrates by padding to provide a concentration of 0.3% or 0.6% solids(based on fabric weight and indicated as SOF (solids on fabric)) anddrying the samples at 150° C. during 3 minutes. Test substrates used inthe Examples were based on polyester/cotton 67/33 blends (PES/CO), whichwere commercially available from Arlitex, Avelgem, Belgium.

After drying, the substrates were tested for their stain release andrepellency properties.

Respective data of stain release, water and oil repellency shown in theExamples and Comparative Examples were based on the following methods ofmeasurement and evaluation criteria:

Stain Release Test

The stain release test was performed using two types of stains:

Dirty Motor Oil (DMO) obtained from General Motors Garage Houttequiet,Beveren; Belgium;

Tea: obtained by immersing a Lipton™ yellow teabag in 165 ml of water at65° C. for 3 minutes.

Staining Procedure 1: Drop Method

10 cm×10 cm test samples were stained with 3 drops DMO or tea. Thesamples were equilibrated at room temperature during 24 hours afterwhich the degree of staining was evaluated by measuring the differencein reflection of a stained versus unstained sample, using a Minoltacolor meter (Lamp D65). An average of 3 measurements were done for eachstain, resulting in a ΔL_(IN) value.

Staining Procedure 2: Brush Method

For this procedure, 0.35 ml DMO or 0.5 ml tea were placed on 10 cm×10 cmtest samples. The stain was brushed into the fabric by brushing 3 timesaround in a plastic holder of 5 cm diameter placed around the stainingliquid. The reflection measurement was done as described above.

Laundering Procedure

The test samples were pinned on a PES/CO ballast of 3 kg and launderedin a Miele washing machine type W 832. A commercial detergent (20 g/kgClax 100, available from Diversy Lever) was added and the substrateswere washed at 70° C., using the main washing program, followed by fourrinse cycles and centrifuging. The samples were dried in a tumble dryerand ironed at 150° C. for 15 seconds. Unstained samples were treated thesame way. The samples were measured with the Minolta meter and comparedto unstained samples, resulting in a ΔL_(LD70° C.) value.

The less negative value for ΔL_(LD70° C.) obtained compared to ΔL_(IN),the better the stain release properties were. %ΔΔL, calculated accordingto formula %ΔΔL=(ΔL_(IN)−ΔL_(LD70° C.)/ΔL_(IN))×100 gave an indicationof the percentage of stain removed during the laundering process. Thehigher the value, the better the stain removal.

Water Repellency Test (WR)

The water repellency (WR) of a substrate was measured using a series ofwater-isopropyl alcohol test liquids and was expressed in terms of the“WR” rating of the treated substrate. The WR rating corresponded to themost penetrating test liquid which did not penetrate or wet thesubstrate surface after 15 seconds exposure. Substrates which werepenetrated by or were resistant only to 100% water (0% isopropylalcohol), the least penetrating test liquid, were given a rating of 0,whereas substrates resistant to a test liquid of 100% isopropyl alcohol(0% water), the most penetrating test liquid, were given a rating of 10.Other intermediate ratings were calculated by dividing the percentisopropyl alcohol in the test liquid by 10, e.g., a treated substrateresistant to a 70%/30% isopropyl alcohol/water blend, but not to an80%/20% blend, would be given a rating of 7.

Oil Repellency (OR)

The oil repellency of a substrate was measured by the AmericanAssociation of Textile Chemists and Colorists (AATCC) Standard TestMethod No. 118-1983, which test was based on the resistance of a treatedsubstrate to penetration by oils of varying surface tensions. Treatedsubstrates resistant only to Nujol® mineral oil (the least penetratingof the test oils) were given a rating of 1, whereas treated substratesresistant to heptane (the most penetrating of the test liquids) weregiven a rating of 8. Other intermediate values were determined by use ofother pure oils or mixtures of oils, as shown in the following Table.

Standard Test Liquids AATCC Oil Repellency Rating Number Compositions 1Nujol ® 2 Nujol ®/n-Hexadecane 65/35 3 n-Hexadecane 4 n-Tetradecane 5n-Dodecane 6 n-Decane 7 n-Octane 8 n-Heptane

Abbreviations

The following abbreviations and trade names were used in the Examplesand Comparative Examples:

EtOAc: ethylacetate

RSH: 2-mercapto ethanol

AIBN: azo(bis)isobutyronitrile

MEFOSEA: N-methyl perfluorooctyl sulfonamido ethyl acrylate

TEL AC812: Fluowet AC812, telomer-type fluorochemical acrylate

C_(n)F_(2n+1)CH₂CH₂OC(O)CH═CH₂, available from Hoechst AG, Germany

PEG²⁰⁰⁻⁸⁰⁰⁰: polyethyleneglycol, superscript number being indicative ofthe molecular weight (Mw), available from Huls, Germany

PEG³⁵⁰-MA: polyethyleneglycol methacrylate, superscript number beingindicative of Mw, available from Inspec, Belgium

MPEG⁷⁵⁰-A: acrylate from polyethylene glycol methyl ether, superscriptnumber being indicative of Mw, available from Inspec, Belgium

MPEG³⁵⁰⁻⁵⁵⁰-M: polyethylene glycol methyl ether methacrylate, thesuperscript number being indicative of Mw, available from Inspec,Belgium

PEG⁴⁶⁸-A: Polyethylene glycol acrylate, the superscript number beingindicative of Mw, available from Inspec, Belgium

IPA: isopropyl alcohol

TEA: triethylamine

HOEMA: 2-hydroxyethyl methacrylate

GMA: glycidyl methacrylate (2,3-epoxypropyl methacrylate)

BO: 2-butanone oxime

IPDI: isophorone diisocyanate

TDI: toluene diisocyanate

DBTDL: dibutyltin dilaurate

MEHQ: methylhydroquinone

Arquad T-50: tallow trimethyl ammonium chloride, available from Akzo,Littleborough, UK

PVA: polyvinyl alcohol

Mowiol™: polyvinyl alcohol available from Hoechst, with various weightaverage molecular weights and degree of hydrolysis as indicated in thetable:

Mowiol ™ Type Degree of Hydrolysis Molecular Weight Mowiol ™ 3-83 83  14000 Mowiol ™ 4-98 98  27 000 Mowiol ™ 5-88 88  35 000 Mowiol ™ 28-98 98145 000 Mowiol ™ 26-88 88 160 000 Mowiol ™ 40-88 88 205 000

Polyviol™ V03/180: polyvinyl alcohol, with a degree of hydrolysis of 82,viscosity (Höppler) of a 4% solution in water at 20° C. in mPas of3+/−0.5, available from Wacker-Chemie.

Polyviol™ W25/190: polyvinyl alcohol with a degree of hydrolysis of 81,and viscosity (Höppler) of a 4% solution in water at 20° C. in mPas of25+/−1.5, available from Wacker-Chemie.

BA: n-butylacrylate

MAA: methacrylic acid

NaOH: sodium hydroxide

MAP 1: (meth)acrylic polymer BA/MAA 18.6/81.4, prepared according to thefollowing procedure:

To a 1 liter 3-necked flask equipped with a reflux condenser, mechanicalstirrer and thermometer, were charged 7.0 g of sulfated castor oilsolution (70% aqueous solution) and 515.0 g of deionized water. Theresulting solution was heated to 95° C., and to this solution were addedsimultaneously and dropwise over a period of about 2 hours: 198.0 g ofmetbacrylic acid, 45.2 g of n-butyl acrylate and an aqueous solutionconsisting of 21.6 g ammonium persulfate dissolved in 50 g of deionizedwater. The reaction mixture was stirred for 3 hours at 90° C., then wasallowed to cool to 50° C. with continued stirring. The resultingcopolymer solution was partially neutralized by adding 25.2 g of 20%aqueous NaOH to give a 33% (wt) polycarboxylate polymer aqueous solutionwith 5.5 equivalents of sodium cation per 100 equivalents of carboxylateanion.

MAP 2: (meth)acrylic polymer BA/MAA 75/25, prepared according to thefollowing procedure:

A polymerization flask was charged with 12.5 g methacrylic acid, 37.5 gbutylacrylate and 1 g sulphated castor oil. After addition of 200 gwater and 30 g acetone, the reaction mixture was degassed usingnitrogen. 0.5 g (NH₄)₂S₂O₂ initiator was added. The polymerization wasrun in a launder-o-meter at 75° C., during 10 hours. The conversion waschecked using GLC and the solvent was removed by evaporation. 5% of themethacrylic acid was neutralised with sodium hydroxide.

MAP 3: (meth)acrylic polymer BA/MAA 50/50, prepared according to asimilar procedure as described for MAP 2, starting from 20 g methacrylicacid and 20 g butylacrylate.

Culminal™: Culminal™ MHPC 50, a methylhydroxypropyl cellulose availablefrom Aqualon

Klucel™: Klucel™ M, a hydroxypropyl cellulose, with 2% Brookfieldviscosity of 5000 mPas., available from Aqualon.

All parts, ratios, percentages etc. in the following examples are byweight unless otherwise noted.

A. Synthesis of Fluorochemical Urethane Acrylate Monomers (FM)

The fluorochemical urethane acrylate monomers (FM) listed in Table 2were prepared according to the general procedure as described below.

1. Synthesis of Fluorochemical Urethane Acrylate Monomers ComprisingPolyoxyalkylene Chains

The synthesis of fluorochemical urethane acrylate monomers comprisingpolyoxyalkylene chains was done in 3 steps, and is exemplified by thesynthesis of HOEMA/IPDI-PEG³⁰⁰⁰-IPDI/HFO-1 (FM-7 in Table 2). Thesynthesis of other fluorochemical urethane acrylate monomers comprisingpolyoxyalkylene chains was carried out similar to the procedure forFM-7.

a. Synthesis of Hydroxyterminated Fluorochemical Oligomers (HFO)

Hydroxy terminated fluorochemical oligomers (HFO) as given in Table 1were made similar to the synthesis of MEFOSEA/RSH 4/1 (indicated asHFO-1 in Table 1) set forth hereafter.

A round bottom flask equipped with two reflux condensors, a stirrer, atemperature control, a nitrogen inlet and a vacuo outlet was chargedwith 2.4 moles MEFOSEA and 987 g EtOAc. The mixture was heated at 40° C.until all fluorochemical monomer was dissolved. 0.6 moles2-mercaptoethanol and 0.15% AIBN were added. The reaction mixture wasgradually heated to 80° C. The reaction was run under nitrogenatmosphere at 80° C. for 16 hours, after which more than 95% conversionwas obtained.

TABLE 1 Composition of hydroxy terminated fluorochemical oligomers (HFO)HFO Composition Ratio HFO-1 MEFOSEA/RSH 4/1 HFO-2 MEFOSEA/RSH 8/1 HFO-3TEL A812/RSH 4/1

b. Synthesis of IPDI/HFO-1

A round bottom flask equipped with a condensor, a stirrer and atemperature control was charged with 100.9 g HFO-1, 8.9 g IPDI and 165 gEtOAc. The reaction mixture was heated at 65° C. until all chemicalswere dissolved. 3 drops DBTDL were added and the reaction was run at 70°C. during 6 hours.

c. Synthesis of HOEMA/IPDI (1/1)

A round bottom flask equipped with a condensor, a stirrer and atemperature control was charged with 5.21 g HOEMA, 8.9 g IPDI and 22 gEtOAc. 2 drops DBTDL and 0.01 g MEHQ were added and the reaction was runat 65° C. for 6 hours.

d. Synthesis of HOEMA/IPDI-PEG³⁰⁰⁰-IPD/HFO-1

A round bottom flask equipped with a stirrer, a condenser and atemperature control was charged with 13.72 g IPDI/HFO-1 (obtained understep A.1.b), 1.76 g HOEMA/IDPI (obtained under step A.1.c), 15 g PG³⁰⁰⁰and 23 g EtOAc. The reaction mixture was heated to 70° C. Four dropsDBTDL, 2 drops TEA and 0.01 g MEHQ were added. The reaction was run at75° C. for 16 hours, after which all isocyanate groups had reacted.

2. Synthesis of Fluorochemical Urethane Acrylate Monomers, NotComprising Polyoxyalkylene Chains

Fluorochemical urethane acrylate monomers not comprising apolyoxyalkylene chain (Table 2), were made using a procedure similar tothe synthesis of HOEMA/IPDI/HFO-1 in equimolar ratio (FM-10, Table 2)which is hereafter described.

A round bottom flask equipped with a condensor, a mechanical stirrer anda temperature control was charged with 100.9 g HFO-1, 8.9 g IPDI, 173 gEtOAc, 5.21 g HOEMA and 0.06 g MEHQ. The reaction mixture was heated at65° C. until all chemicals were dissolved. 4 drops stannous octanoatewere added and the reaction was run at 75° C. for 16 hours.

TABLE 2 Composition of Fluorochemical Urethane Acrylate Monomers (FM)Composition of Fluorochemical FM Urethane Acrylate Monomers FM-1HOEMA/IPDI-PEG¹⁰⁰⁰-IPDI/HFO-1 FM-2 HOEMA/TDI-PEG¹⁰⁰⁰-TDI/HFO-1 FM-3HOEMA/IPDI-PEG⁸⁰⁰-IPDI/HFO-1 FM-4 HOEMA/IPDI-PEG²⁰⁰⁰-IPDI/HFO-1 FM-5HOEMA/IPDI-PEG²⁰⁰⁰-IPDI/HFO-2 FM-6 HOEMA/IPDI-PEG⁴⁰⁰⁰-IPDI/HFO-2 FM-7HOEMA/IPDI-PEG³⁰⁰⁰-IPDI/HFO-1 FM-8 HOEMA/IPDI-PEG⁴⁰⁰⁰-IPDI/HFO-1 FM-9HOEMA/IPDI-PEG⁸⁰⁰⁰-IPDI/HFO-1 FM-10 HOEMA/IPDI/HFO-1 FM-11HOEMA/IPDI/HFO-3

B. Synthesis of Comonomers

The comonomers which were not commercially available and that were usedin the examples were prepared according to the procedure used tosynthesize HOEMA/IPDI/BO (molar ratio 1/1/1):

A round bottom flask equipped with a mechanical stirrer, a temperaturecontrol, addition funnel, nitrogen inlet and outlet, was charged with111 g IPDI, 65 g HOEMA, 200 g EtOAc, 0.1 g phenotiazin, 0.1 g MEHQ and0.2 g dibutyl tin dilaurate. The reaction mixture was slowly heated toabout 50° C. A solution of 44 g 2-butanone oxime, dissolved in 20 gEtOAc was slowly added over a period of 1 hour. Then the reactionmixture was stirred at 72° C. for 6 hours. IR analysis indicated thatall isocyanate groups had reacted.

This procedure was also used for the synthesis of PEG³⁵⁰-MA/IPDI/BO(molar ratio 1/1/1) and HOEMA/IDI/BO (molar ratio 1/1/1).

C. Homo or Copolymerization of Fluorochemical Urethane Acrylate Monomers

The fluorochemical urethane acrylate monomers obtained under step A werehomopolymerized or copolymerized with commercially available comonomersor with comonomers prepared as described under the above procedure B ina reaction flask equipped with a mechanical stirrer, a condenser and atemperature control. 0.375% AIBN was added and the reaction was run at75° C. for 10 to 16 hours. A second charge of 0.18% AIBN was added andthe reaction was continued for 6 hours at a temperature of 75° C. Theorganic solution was added to a water phase containing 3% emulsifiersuch as Arquad T-50. After homogenisation with an ultrasonic probe(Branson 250 sonifier), the organic solvent was removed by evaporationand an emulsion was obtained.

The composition of the polymers prepared under step C is given in Table3.

TABLE 3 Composition of Fluorochemical Compounds (FC) RatioFluorochemical by % FC Monomer Comonomer(s) Weight Solids FC-1 FM-1 — —15 FC-2 FM-2 — — 15 FC-3 FM-2 (HOEMA/TDI/BO) 90/10 15 FC-4 FM-3 — — 20FC-5 FM-4 — — 20 FC-6 FM-5 — — 20 FC-7 FM-1 GMA 95/5 20 FC-8 FM-1(HOEMA/IPDI/BO) 95/5 20 FC-9 FM-1 PEG³⁵⁰-MA 90/10 20 FC-10 FM-1MPEG⁴³⁰-MA 90/10 20 FC-11 FM-1 (PEG³⁵⁰- 90/10 15 MA/IPDI/BO) FC-12 FM-6— — 20 FC-13 FM-7 — — 10 FC-14 FM-8 — — 10 FC-15 FM-9 — — 10 FC-16 FM-10MPEG⁴³⁰-MA 80/20 15 FC-17 FM-10 PEG³⁵⁰-MA 80/20 15 FC-18 FM-11 PEG³⁵⁰-MA80/20 15 FC-19 FM-11 MPEG⁴³⁰-MA 80/20 15 FC-20 FM-11 PEG³⁵⁰-MA/GMA75/20/5 15 FC-21 FM-11 PEG³⁵⁰- 75/20/5 15 MA/(HOEMA/IPDI/BO) FC-22 FM-10PEG³⁵⁰-MA 90/10 15 FC-23 FM-10 PEG³⁵⁰-MA 80/20 15 FC-24 FM-10 PEG³⁵⁰-MA70/30 15 FC-25 FM-10 PEG³⁵⁰-MA/GMA 75/20/5 15 FC-26 FM-10 PEG³⁵⁰-75/20/5 15 MA(HOEMA/IPDI/BO) FC-27 FM-10 MPEG⁴³⁰-MA 80/20 15 FC-28 FM-11MPEG⁴³⁰-MA 50/50 15 FC-29 FM-11 MPEG⁵⁵⁰-MA 50/50 15 FC-30 FM-11MPEG⁷⁵⁰-A 50/50 15 FC-31 FM-10 PEG⁴⁶⁸-A/GMA 50/45/5 15 FC-32 FM-10MPEG⁴³⁰-MA 50/50 15 FC-33 FM-10 MPEG⁵⁵⁰-MA 50/50 15 FC-34 FM-10MPEG⁷⁵⁰-A 50/50 15 FC-35 FM-11 MPEG⁷⁵⁰-A 30/70 20 FC-36 FM-11 MPEG⁵⁵⁰-MA30/70 10 FC-37 FM-11 MPEG⁴³⁰-MA 30/70 10

Examples 1 to 25 and Comparative Example C-1

In Examples 1 to 25, fluorochemical compounds were prepared andemulsified according to the general procedure described above.Polyester/cotton blends were treated with the fluorochemical compoundsso as to give 0.3 or 0.6% SOF. After treatment, the fabrics were driedat 150° C. for 3 minutes. The treated PES/CO substrates were stainedwith dirty motor oil using the drop method. Comparative Example C-1 wasmade with untreated PES/CO. The results of stain release and oil andwater repellency are given in Table 4.

TABLE 4 DMO (Drop Method) Stain Release and Repellent Properties InitialPer- Stain Release Color Ex Fluorochemical % formance Measurement NoCompound SOF OR WR ΔL_(IN) ΔL_(LD70° C.) % ΔΔL 1 FC-1 0.3 5 9 −5.57−0.63 89 2 FC-1 0.6 5 9 −7.21 −0.49 93 3 FC-2 0.3 5 7 −4.4 −1.12 75 4FC-2 0.6 5 8 −5.26 −0.84 84 5 FC-3 0.3 6 5 −10.08 −5.07 50 6 FC-3 0.6 66 −3.19 −1.26 61 7 FC-16 0.3 3 4 −6.56 −2.45 63 8 FC-17 0.3 4 5 −9.84−3.02 69 9 FC-17 0.6 5 7 −8.77 −0.24 97 10 FC-18 0.3 6 5 −11.46 −3.5 6911 FC-18 0.6 6 8 −8.9 −1.2 87 12 FC-19 0.3 6 4 −10.9 −4.09 62 13 FC-190.6 6 7 −10.83 −2.91 73 14 FC-20 0.3 6 4 −10.5 −5.16 51 15 FC-20 0.6 6 4−8.17 −3.3 60 16 FC-21 0.6 6 4 −11 −5.08 54 17 FC-22 0.3 6 9 −12.94−6.38 51 18 FC-22 0.6 6 8 −7.05 −2.53 64 19 FC-23 0.6 6 9 −7.36 −1.55 7920 FC-24 0.3 6 9 −9.48 −2.48 74 21 FC-24 0.6 6 9 −10.93 −3.91 64 22FC-25 0.6 6 7 −9.47 −4.62 51 23 FC-26 0.3 6 8 −7.89 −3.68 53 24 FC-270.3 6 8 −6.99 −1.62 77 25 FC-27 0.6 6 9 −8.96 −2.94 67 C-1 — — 0 0−15.45 −9.56 38

The data shows that good to very good DMO stain release properties wereobtained using the fluorochemical compositions of the invention. Theoptimal amount of fluorochemical compound needed to treat the substratedepends on the particular fluorochemical composition used. It canfurther be seen that not only was good stain release obtained, but alltreated PES/CO substrates show remarkable high oil and especially highwater repellencies, indicating that the compositions are suitable foruse as fluorochemical repellent agents. This is a further advantage overthe untreated samples which show no oil or water repellency at all.

Examples 26 to 54 and Comparative Example C-2

In Examples 26 to 54 the same type of experiment was repeated but thistime the DMO was applied to the fabric by the brush method. ComparativeExample C-2 was made with untreated PES/CO substrate. The results ofstain release and oil and water repellency are given in Table 5.

TABLE 5 DMO Stain Release (Brush) and Oil and Water Repellency InitialPer- Stain Release Color Ex Fluorochemical % formance Measurement NoCompound SOF OR WR ΔL_(IN) ΔL_(LD70° C.) % ΔΔL 26 FC-1 0.6 6 10 −17.79−4.31 76 27 FC-4 0.6 6 10 −17.99 −6.47 64 28 FC-5 0.6 5 9 −18 −3.54 8029 FC-6 0.6 4 5 −17.87 −7.58 58 30 FC-7 0.6 6 10 −17.71 −5.95 66 31 FC-80.6 6 10 −18.1 −7.08 61 32 FC-9 0.6 6 10 −18.22 −7.38 59 33 FC-10 0.6 610 −18.14 −5.37 70 34 FC-11 0.6 6 6 −17.98 −3.49 81 35 FC-12 0.6 4 3−18.44 −8.08 56 36 FC-13 0.3 6 10 −18.15 −3.95 78 37 FC-14 0.6 5 3−18.95 −7.76 59 38 FC-15 0.3 1 0 −16.83 −7.91 53 39 FC-17 0.6 6 9 −17.9−8.33 53 40 FC-18 0.6 7 3 −17.32 −8.61 50 41 FC-19 0.6 6 5 −17.79 −6.4864 42 FC-20 0.6 6 6 −17.59 −9.08 48 43 FC-25 0.6 6 9 −17.81 −11.82 34 44FC-27 0.6 6 6 −17.8 −11.48 36 45 FC-28 0.6 6 4 −17.43 −5.97 66 46 FC-290.6 6 3 −18.06 −7.54 58 47 FC-30 0.6 5 4 −18.81 −8.4 55 48 FC-31 0.6 6 9−18.18 −11.17 39 49 FC-32 0.6 6 6 −17.7 −10.09 43 50 FC-33 0.6 5 5−18.34 −9.87 46 51 FC-34 0.6 4 5 −17.43 −9.05 48 52 FC-35 0.6 5 2 −18.33−7.21 61 53 FC-36 0.6 6 1 −18.74 −10.1 46 54 FC-37 0.6 5 3 −18.88 −6.0568 C-2 — — 0 0 −15.32 −10.18 34

In this more demanding test, most of the treated substrates performedbetter than the untreated sample as shown by the less negative values ofΔL_(LD70° C.) for most treated samples. In addition to good DMO stainrelease, the treated samples showed high oil and water repellency.

Examples 55 to 70 and Comparative Example C-3

In Examples 55 to 70, PES/CO blends treated with the fluorochemicalcompounds according to the invention were stained with tea using thedrop method. Comparative Example C-3 was made with untreated fabric. Theresults of stain release and oil and water repellency are given in Table6.

TABLE 6 Stain Release (Tea-Drop) and Repellency Properties of PES/COInitial Per- Stain Release Color Ex Fluorochemical % formanceMeasurement No Compound SOF OR WR ΔL_(IN) ΔL_(LD70° C.) % ΔΔL 55 FC-10.3 5 9 −6.14 −0.76 88 56 FC-2 0.3 5 7 −6.13 −0.75 88 57 FC-3 0.3 6 5−6.34 −1.14 82 58 FC-16 0.6 5 3 −6.27 −0.65 90 59 FC-17 0.3 4 5 −6.91−0.77 89 60 FC-17 0.6 5 7 −5.67 −0.4 93 61 FC-18 0.6 6 8 −8.41 −1.91 7762 FC-19 0.6 6 7 −6.97 −2.91 58 63 FC-20 0.6 6 4 −6.23 −1.94 69 64 FC-210.6 6 4 −4.98 −2.09 58 65 FC-22 0.3 6 9 −7.84 −1.04 87 66 FC-23 0.3 6 9−7.68 −1.09 86 67 FC-24 0.3 6 9 −9.69 −1.37 86 68 FC-25 0.3 6 8 −7.65−0.75 90 69 FC-26 0.3 6 8 −7.46 −1.36 82 70 FC-27 0.3 6 8 −7.74 −1.48 81C-3 — — 0 0 −2.32 −0.91 61

The results show that the fluorochemical compositions can also improvethe tea stain release properties of a PES/CO substrate. High tea stainremoval was observed, in several cases about 90% of the tea stain couldbe removed.

Examples 71 to 103 and Comparative Example C-4

In Examples 71 to 103, treated PES/CO substrates were tested with teastains, but now using the brush method. Comparative Example C-4 was madewith untrated PES/CO substrate. The results of stain release and oil andwater repellency are given in Table 7.

TABLE 7 Tea Stain Release Using Brush Method Initial Per- Stain ReleaseColor Ex Fluorochemical % formance Measurement No Compound SOF OR WRΔL_(IN) ΔL_(LD70° C.) % ΔΔL 71 FC-1 0.3 6 10 −1.45 −0.75 48 72 FC-1 0.66 10 −1.47 −0.41 72 73 FC-4 0.3 5 9 −1.74 −0.88 49 74 FC-4 0.6 6 10−1.65 −0.81 51 75 FC-5 0.6 5 9 −1.89 −0.79 58 76 FC-6 0.3 3 3 −2.09−0.76 64 77 FC-6 0.6 4 5 −1.69 −0.46 73 78 FC-7 0.6 6 10 −1.83 −0.77 5879 FC-8 0.6 6 10 −1.99 −0.84 58 80 FC-9 0.6 6 10 −1.75 −0.67 62 81 FC-100.6 6 10 −1.91 −0.66 65 82 FC-11 0.6 6 6 −1.93 −0.7 64 83 FC-12 0.6 4 3−2.09 −1.03 51 84 FC-13 0.6 6 10 −2.86 −0.98 66 85 FC-14 0.6 5 3 −2.77−0.84 70 86 FC-15 0.6 2 0 −3.11 −0.54 83 87 FC-17 0.6 6 9 −1.46 −0.68 5388 FC-18 0.6 6 8 −8.41 −1.91 77 89 FC-19 0.6 6 5 −2.55 −0.93 64 90 FC-200.6 6 6 −1.52 −1.01 34 91 FC-25 0.6 6 9 −1.5 −1.05 30 92 FC-27 0.3 6 6−1.43 −0.91 36 93 FC-28 0.6 6 4 −2.02 −0.79 61 94 FC-29 0.6 6 3 −2.33−1.19 49 95 FC-30 0.6 5 4 −2.19 −1.22 44 96 FC-31 0.3 6 9 −1.69 −1.37 1997 FC-32 0.3 6 6 −1.43 −0.91 36 98 FC-33 0.3 4 5 −1.63 −1.34 18 99 FC-340.6 4 5 −1.97 −0.9 54 100 FC-35 0.6 5 2 −2.68 −0.85 68 101 FC-36 0.3 4 0−3.15 −1.2 62 102 FC-37 0.3 2 2 −3.28 −0.99 70 103 FC-37 0.6 5 3 −2.04−0.61 70 C-4 — — 0 0 −2.62 −1.22 53

Most of the treated substrates perform better or at least as good asuntreated material for tea stain release. Moreover, they show high waterand oil repellency. Depending on the method used to stain thesubstrates, other results were obtained. While some formulations havelower stain release properties as untreated samples in this test, theyshowed good or excellent performance in the drop method. For example,fluorochemicals FC-20, 25 and 27 (used in Examples 90-92), showed lowtea stain release using the brush method, but very high tea stainrelease using the drop method (Examples 63, 68 and 70).

Examples 104 to 111 and Comparative Example C-5

In Examples 104 to 111, PES/CO substrate was treated with fluorochemicalcompound FC-37 (Example 104) or with a 50/50 blend of FC-37 with variouspolyvinyl alcohols as reported in Table 8 (Examples 105 to 111). Thesubstrate was treated in such a way as to have 0.6% SOF fluorochemicalcompound and 0.6% SOF polyvinyl alcohol (except Example 104).Comparative Example C-5 was made using untreated PES/CO. The treated anduntreated substrates were stained with DMO (brush) and tested for theirstain release and repellency properties. The results are given in Table8.

TABLE 8 Stain Release for DMO Stains Initial Stain Release Colour ExPerformance Measurement* No PVA OR WR ΔL_(IN) ΔL_(LD70° C.) % ΔΔL 104 —4 1 −58.8 −14.6 75 105 Mowiol ™ 3-83 5 0 −56.1 −14.3 75 106 Mowiol ™4-98 6 1 −57.8 −9.1 84 107 Mowiol ™ 5-88 4 1 −55.5 −13.0 77 108 Mowiol ™28-99 6 1 −56.4 −5.9 89 109 Mowiol ™ 26-88 6 0 −56.0 −11.0 80 110Polyviol ™ V03/180 3 0 −55.3 −13.2 76 111 Polyviol ™ W25/190 4 1 −51.5−9.9 81 C-5 — 0 0 −45.0 −21.9 51 Note: *lens opening of the Minoltacolorimeter was set at 53 mm

From the results it can be concluded that the good stain releaseproperties provided by the fluorochemical compound alone could furtherbe improved by the addition of a polyvinyl alcohol. In some cases, animprovement in oil repellency was noticed as well.

Examples 112 to 119

In Examples 112 to 119, PES/CO substrate was treated with fluorochemicalds FC-17 and FC-35 or with a 50/50 blend of the fluorochemical compoundand polyvinyl alcohol Mowiol™ 3-83. The substrate was treated in such away as to have 0.6% fluorochemical compound and 0.6% SOF polyvinylalcohol. The treated substrates were stained with Tea or DMO (brush) andtested for their stain release and oil and water repellency properties.The results are reported in Table 9.

TABLE 9 Stain Release for Tea and DMO Stains Initial Stain ReleaseColour FC Per- Measurement Ex com- formance % No pound PVA OR WR ΔL_(IN)ΔL_(LD70° C.) ΔΔL Stain: TEA 112 FC-17 — 6 6 −2.5 −1.1 55 113 FC-17Mowiol ™ 3-83 5 2 −2.7 −0.9 67 114 FC-35 — 5 2 −2.9 −1.3 56 115 FC-35Mowiol ™ 3-83 5 0 −2.6 −0.8 70 Stain: DMO 116 FC-17 — 6 6 −16.8 −8.7 48117 FC-17 Mowiol ™ 3-83 5 2 −16.4 −7.1 57 118 FC-35 — 5 2 −17.0 −6.1 64119 FC-35 Mowiol ™ 3-83 5 0 −17.8 −4.9 72

The results show that improved stain release performance can be obtainedby blending polyvinyl alcohol with the fluorochemical compound. Littleor no influence on oil repellency, but some decrease in water repellencywas observed.

Examples 120 to 129 and Comparative Examples C-6 and C-7

In Examples 120 to 129, PES/CO substrate was treated with fluorochemicalcompound FC-37 or with a 50/50 blend of FC-37 with polyvinyl alcohol, asshown in Table 10. The substrate was treated in such a way as to have0.6% SOF fluorochemical compound or 0.6% SOF fluorochemical compound and0.6% SOF polyvinyl alcohol. Comparative Examples C-6 and C-7 were madeusing untreated PES/CO. The treated and untreated substrates werestained with tea or wine and tested for their stain release andrepellency properties. The results are reported in Table 10.

TABLE 10 Initial Stain Release Ex Performance Performance* No Polyvinylalcohol OR WR ΔL_(IN) ΔL_(LD70° C.) % ΔΔL Stain: TEA 120 — 4 1 −7.4 −1.777 121 Mowiol ™ 3-83 5 0 −7.0 −1.3 81 122 Mowiol ™ 5-88 4 1 −6.4 −1.2780 123 Polyviol ™ V03/180 3 0 −6.4 −1.03 84 124 Polyviol ™ W25/190 4 1−6.1 −1.2 81 C-6 — 0 0 −6.3 −3.4 46 Stain: WINE 125 — 4 1 −12.5 −1.2 90126 Mowiol ™ 3-83 5 0 −12.4 −0.9 93 127 Mowiol ™ 5-88 4 1 −12.6 −1.1 91128 Polyviol ™ V03/180 3 0 −13.9 −0.7 95 129 Polyviol ™ W25/190 4 1−11.4 −0.8 93 C-7 — 0 0 −13.4 −3.5 74 Note: *lens opening of the Minoltacolorimeter was set at 53 mm instead of 18 mm

As can be seen from the above table, the addition of polyvinyl alcoholto the fluorochemical composition also slightly improves the stainrelease performance of the composition relative to aqueous based stains.

Examples 130 to 147

In Examples 130 to 147, PES/CO substrate was treated with fluorochemicalcompounds FC-17, FC-35 or FC-37 or with a 50/50 blend of thefluorochemical compound with Culminal™ MHPC 50 or Klucel™ M, as given inTable 11. The substrate was treated in such a way as to have 0.6% SOFfluorochemical compound or 0.6% SOF fluorochemical compound and 0.6% SOFCellulose derivative. The treated substrates were stained with tea orDMO (brush) and tested for their stain release and repellencyproperties. The results are given in Table 11.

TABLE 11 Initial Stain Release Color Fluoro- Per- Measurement Exchemical Cellulose formance % No Compound Derivative OR WR ΔL_(IN)ΔL_(LD70° C.) ΔΔL Stain: TEA 130 FC-17 — — — −2.5 −1.1 55 131 FC-17Culminal ™ 6 8 −2.3 −1.0 57 132 FC-17 Klucel ™ 6 8 −2.7 −0.9 66 133FC-35 — — — −2.9 −1.3 56 134 FC-35 Culminal ™ 5 2 −2.7 −0.9 69 135 FC-35Klucel ™ 5 0 −3.2 −0.9 72 136 FC-37 — — — −2.4 −0.7 71 137 FC-37Culminal ™ 2 0 −2.5 −0.9 63 138 FC-37 Klucel ™ 6 0 −3.1 −0.8 74 Stain:DMO 139 FC-17 — — — −16.8 −8.7 48 140 FC-17 Culminal ™ 6 8 −16.2 −5.1 69141 FC-17 Klucel ™ 6 8 −16.3 −3.0 81 142 FC-35 — — — −17.0 −6.1 64 143FC-35 Culminal ™ 5 2 −17.3 −4.3 75 144 FC-35 Klucel ™ 5 0 −17.7 −5.2 71145 FC-37 — — — −17.9 −4.6 74 146 FC-37 Culminal ™ 2 0 −16.7 −4.9 71 147FC-37 Klucel ™ 6 0 −16.8 −1.1 93

The results for Examples 130 to 147 show that the stain releaseproperties can also be improved by using a non-ionic cellulose ether inthe fluorochemical composition.

Examples 148 to 167

In Examples 148 to 167, PES/CO substrate was treated with fluorochemicalcompounds FC-17, FC-35 or FC-37 or with a 50/50 blend of thefluorochemical compound with (meth)acrylic polymers as shown in Table12. The substrate was treated in such a way as to have 0.6% SOFfluorochemical compound or 0.6% SOF fluorochemical compound and 0.6% SOF(meth)acrylic polymer. The treated substrates were stained with tea orDMO and tested for their stain release and repellency properties (brushmethod). The results are shown in Table 12.

TABLE 12 Fluoro- Initial Stain Release Color chemical Per- MeasurementEx Com- (Meth)acrylic formance % No pound Polymer OR WR ΔL_(IN)ΔL_(LD70° C.) ΔΔL Stain: TEA 148 FC-17 — — — −2.5 −1.1 55 149 FC-17 MAP1 5 4 −2.2 −1.3 43 150 FC-17 MAP 2 6 8 −2.5 −1.1 56 151 FC-35 — — — −2.9−1.3 56 152 FC-35 MAP 1 5 0 −2.6 −0.8 70 153 FC-35 MAP 2 5 1 −2.6 −0.966 154 FC-35 MAP 3 5 3 −2.4 −0.9 62 155 FC-37 — — — −2.4 −0.7 71 156FC-37 MAP 1 6 1 −1.9 −0.4 78 157 FC-37 MAP 2 6 1 −2.4 −0.8 66 Stain: DMO158 FC-17 — — — −16.8 −8.7 48 159 FC-17 MAP 1 5 4 −16.5 −4.3 74 160FC-17 MAP 2 6 8 −16.6 −4.7 71 161 FC-35 — — — −17.0 −6.1 64 162 FC-35MAP 1 5 0 −17.2 −5.3 69 163 FC-35 MAP 2 5 1 −17.7 −6.3 64 164 FC-35 MAP3 5 3 −17.7 −5.2 70 165 FC-37 — — — −17.9 −4.6 74 166 FC-37 MAP 1 6 1−17.4 −3.5 80 167 FC-37 MAP 2 6 1 −17.1 −4.8 72

Especially for DMO stains, stain release could be improved by adding acopolymer of an alkyl (meth)acrylate and (meth)acrylic acid to thefluorochemical composition.

Examples 168 to 197

In Examples 168 to 197, PES/CO substrate was treated with fluorochemicalcompounds FC-17, FC-35 or FC-37 or with a 50/50 blend of thefluorochemical compound with polyethyleneglycol of various molecularweight, as given in Table 13. The fluorochemical compound and thepolyethyleneglycol (when used) were applied at 0.6% SOF each. Thetreated substrates were stained with DMO or tea and tested for theirstain release properties (brush method). The results are shown in Table13.

TABLE 13 Stain Release Colour Measurement* Ex No FC PEG ΔL_(IN)ΔL_(LD70° C.) % ΔΔL Stain: DMO 168 FC-17 — −58.5 −18.1 69 169 FC-17 PEG200 −58.2 −16.5 72 170 FC-17 PEG 1000 −56.9 −12.5 78 171 FC-17 PEG 2000−53.5 −8.1 85 172 FC-17 PEG 4000 −57.3 −16.8 71 173 FC-35 — −54.0 −18.366 174 FC-35 PEG 200 −55.2 −16.7 70 175 FC-35 PEG 1000 −55.0 −16.1 71176 FC-35 PEG 2000 −54.5 −15.8 71 177 FC-35 PEG 4000 −56.9 −16.8 70 178FC-37 — −59.9 −14.3 76 179 FC-37 PEG 200 −56.9 −11.3 80 180 FC-37 PEG1000 −58.4 −13.0 78 181 FC-37 PEG 2000 −58.6 −11.5 80 182 FC-37 PEG 4000−56.6 −10.5 81 Stain: TEA 183 FC-17 — −6.4 −3.0 53 184 FC-17 PEG 200−7.5 −4.0 47 185 FC-17 PEG 1000 −7.0 −3.2 54 186 FC-17 PEG 2000 −6.4−2.9 55 187 FC-17 PEG 4000 −7.0 −3.8 46 188 FC-35 — −6.4 −2.3 64 189FC-35 PEG 200 −6.5 −2.4 63 190 FC-35 PEG 1000 −6.6 −3.1 53 191 FC-35 PEG2000 −6.1 −3.0 51 192 FC-35 PEG 4000 −6.0 −3.2 47 193 FC-37 — −5.7 −2.654 194 FC-37 PEG 200 −4.6 −2.8 58 195 FC-37 PEG 1000 −6.9 −2.8 59 196FC-37 PEG 2000 −6.7 −2.1 69 197 FC-37 PEG 4000 −6.7 −2.4 64 Note: *lensopening of the Minolta colorimeter was set at 53 mm

From the above Table, it can be concluded that the addition ofpolyethyleneglycol to the fluorochemical composition improves the stainrelease properties of the composition for DMO stains but little or noimprovement is noticed relative to aqueous based stains. In certaincases, the addition of polyethyleneglycol appears to have a negativeinfluence on the stain release properties in the case of aqueous basedstains.

What is claimed is:
 1. A method of treatment of a substrate comprisingthe step of contacting said substrate with a fluorochemical compositioncomprising a polymer derived from polymerization of monomercorresponding to the following general formula (I):

wherein: R_(f) is selected from the group consisting of perfluorinatedor partially fluorinated aliphatic groups; L¹ and L² each represent anorganic divalent linking group and can be the same or different; L³represents an organic linking group with a valence of n+1; t is 0 or 1;n is an integer of 2 to 20; A¹ and A² each independently represent adivalent residue obtained by removing two —NCO groups from acorresponding diisocyanate, and can be the same or different; X¹ and X²are each independently selected from the group consisting of O, NH andS; B¹ represents a hydrophilic residue obtained by removing the groupsHX¹ and HX² from a compound HX¹—B¹—X²H that comprises apoly(oxyalkylene) group; G represents a free radical polymerizablegroup; and s is 0 or 1, with the proviso that when s is 0, L² representsa hydrophilic segment comprising a poly(oxyalkylene) group or saidpolymer is derived from a copolymerization of a monomer according toformula (I) and a poly(oxyalkylene) group containing monomer.
 2. Amethod according to claim 1, wherein G is —(O)C—C(CH₃)═CH₂ or—(O)C—CH═CH₂.
 3. A method according to claim 1, wherein L²—G together isa moiety corresponding to the following formula (II):

wherein: X³ and X⁴ are each independently selected from O or NH, R¹represents a linear or branched alkylene group having 2 to 4 carbonatoms or a group containing a poly(oxyalkylene) moiety, and R² ishydrogen or a methyl group.
 4. A method according to claim 1, wherein L¹is selected from the group consisting of:

wherein: R³ represents a linear or branched alkylene group having 2 to 4carbon atoms; and R⁴ represents an alkyl group having 1 to 4 carbonatoms.
 5. A method according to claim 1, wherein L³ corresponds to thefollowing formula:

wherein: n is an integer of 2 to 20; Z represents the residue of a freeradical initiator; R⁵ is hydrogen or a methyl group; X⁵ is S; X⁶ is O orNH; and L⁵ represents an alkylene group having 2 to 4 carbon atoms.
 6. Amethod according to claim 1, wherein said poly(oxyalkylene) groupcontaining monomer copolymerized with the monomer of formula (I)corresponds to the following formula:

wherein: R⁶, R⁷ and R⁸ are each independently selected from the groupconsisting of linear or branched alkylene groups having 2 to 4 carbonatoms; R⁹ is hydrogen or an alkyl group having 1 to 4 carbon atoms; xand y are each independently selected from integers of 0 to 30, providedthe sum of x and y is at least 5; and R¹⁰ is hydrogen or a methyl group.7. A method according to claim 1, wherein said substrate is a fibroussubstrate.
 8. A method according to claim 7, wherein said substratecomprises natural fibers.
 9. A method according to claim 7, wherein saidfibers are selected from the group consisting of cellulose fibers,polyester fibers, and blends thereof.
 10. A method according to claim 7,wherein said substrate is textile or paper.
 11. A method according toclaim 1, wherein the fluorochemical composition further comprises apolymer selected from the group consisting of polyvinyl alcohols,non-ionic cellulose ethers, polyethylene glycols and copolymers of analkyl(meth)acrylate and (meth)acrylic acid.
 12. The method of claim 1wherein s is 0 and L² represents a hydrophilic segment comprising apoly(oxyalkylene) group.
 13. The method of claim 1 wherein the number ofoxyalkylene moieties in said poly(oxyalkylene) group is between 18 and275.
 14. The method of claim 1 wherein s is
 1. 15. A fluorochemicalcomposition comprising a polymer derived from a polymerization of amonomer corresponding to the following general formula (I):

wherein: R_(f) is selected from the group consisting of perfluorinatedor partially fluorinated aliphatic groups; L¹ and L² each independentlyrepresent an organic divalent linking group and may be the same ordifferent; L³ represents an organic linking group having a valence ofn+1; t is 0 or 1; n is an integer of 2 to 20; A¹ and A² eachindependently represent a divalent residue obtained by removing two —NCOgroups from a corresponding diisocyanate and may be the same ordifferent; X¹ and X² are each independently selected from the groupconsisting of O, NH or S; B¹ represents a hydrophilic residue obtainedby removing the groups HX¹ and HX² from a compound HX¹—B¹—X²H thatcomprises a poly(oxyalkylene) group; G represents a free radicalpolymerizable group; and s is 0 or 1, with the proviso that when s is 0,L² represents a hydrophilic segment comprising a poly(oxyalkylene) groupor said polymer is derived from a copolymerization of a monomeraccording to formula (I) and a poly(oxyalkylene) group containingmonomer.
 16. A fluorochemical composition according to claim 15, whereinG is —(O)C—C(CH₃)═CH₂or —(O)C—CH═CH₂.
 17. A fluorochemical compositionaccording to claim 15, wherein L²—G together is a moiety correspondingto the following formula (II):

wherein: X³ and X⁴ are each independently selected from O or NH; R¹represents a linear or branched alkylene group having 1 to 4 carbonatoms or a group containing poly(oxyalkylene) moiety; and R² is hydrogenor a methyl group.
 18. A fluorochemical composition according to claim15, wherein L¹ corresponds to one the following formulas:

wherein R³ represents a linear or branched alkylene group having 2 to 4carbon atoms; and R⁴ represents an alkyl group having 1 to 4 carbonatoms.
 19. A fluorochemical composition according to claim 15, whereinL³ corresponds to the following formula:

wherein: n is an integer of 2 to 20; Z represents the residue of a freeradical initiator; R⁵ is hydrogen or a methyl group; X⁶ is O or NH; andL⁵ is an alkylene group having 2 to 4 carbon atoms.
 20. A fluorochemicalcomposition according to claim 15, wherein said poly(oxyalkylene) groupcontaining monomer copolymerized with the monomer of formula (I)corresponds to the following formula:

wherein: R⁶, R⁷ and R⁸ are each independently selected from the groupconsisting of linear or branched alkylene groups having 2 to 4 carbonatoms; R⁹ is hydrogen or an alkyl group having 1 to 4 carbon atoms; xand y are each independently selected from integers of 0 to 30, providedthe sum of x and y is at least 5; and R¹⁰ is hydrogen or a methyl group.21. A fluorochemical composition according to claim 15, wherein thefluorochemical composition further comprises a polymer selected from thegroup consisting of polyvinyl alcohols, non-ionic cellulose ethers,polyethylene glycols and copolymers of an alkyl(meth)acrylate and(meth)acrylic acid.
 22. A monomer corresponding to the following formula(1):

wherein: R_(f) is selected from the group consisting of partially orperfluorinated aliphatic groups; L¹ and L² each independently representan organic divalent linking group and can be the same or different; L³represents an organic linking group with a valence of n+1; t is 0 or 1;n is an integer of 2 to 20; A¹ and A² each independently represent adivalent residue obtained by removing two —NCO groups from acorresponding diisocyanate and can be the same or different; X¹ and X²are each independently selected from the group consisting of O, NH or S;B¹ represents a hydrophilic residue obtained by removing the groups HX¹and HX² from a compound HX¹—B¹—X²H that comprises a poly(oxyalkylene)group; G represents a free radical polymerizable group; and s is 0 or 1.23. A monomer composition comprising a monomer containing a 25poly(oxyalkylene) group and a monomer according to claim 22 wherein s is0.
 24. A monomer composition according to claim 23, wherein saidpoly(oxyalkylene) group containing monomer corresponds to the followingformula:

wherein: R⁶, R⁷ and R⁸ are each independently selected from the groupconsisting of linear or branched alkylene groups having 2 to 6 carbonatoms; R⁹ is hydrogen or an alkyl group having 1 to 4 carbon atoms; xand y are each independently selected from integers of 0 to 30, providedthe sum of x and y is at least 5; and R¹⁰ is hydrogen or a methyl group.25. A method of treatment of a substrate comprising the step ofcontacting said substrate with a fluorochemical composition comprising apolymer derived from polymerization of monomer corresponding to thefollowing general formula (I):

wherein: R_(f) is selected from the group consisting of perfluorinatedor partially fluorinated aliphatic groups; L¹ and L² each represent anorganic divalent linking group and can be the same or different; L³represents an organic linking group with a valence of n+1; t is 0 or 1;n is an integer of 2 to 20; A¹ and A² each independently represent adivalent residue obtained by removing two —NCO groups from acorresponding diisocyanate, and can be the same or different; X¹ and X²are each independently selected from the group consisting of O, NH andS; B¹ represents a hydrophilic residue obtained by removing the groupsHX¹ and HX² from a compound HX¹—B¹—X²H that comprises apoly(oxyalkylene) group; G represents a free radical polymerizablegroup; and s is 0 or 1, with the proviso that when s is 0, L² representsa hydrophilic segment comprising a poly(oxyalkylene) group.